Environmental forensics: contaminant specific guide

545 Pages·2006·14.317 MB·English

by  Robert D Morrison, Brian Murphy

Foreword
Environmental forensics is the systematic and scientific evaluation of physical, chemical and
historical information for the purpose of developing defensible scientific and legal conclusions
regarding the source or age of a contaminant release into the environment. Within this general
definition, the science of environmental forensics has evolved into a global scientific discipline
with numerous applications.
The purpose of this book is to provide the student or scientist of environmental forensics
with a contaminant-specific resource for investigating and solving the questions of when a
contaminant release occurred, the origin of the release, and a basis for apportioning liability
among multiple responsible parties. The impetus for structuring a book on a contaminant-
specific approach rather than a methodological or analytical perspective is to provide the
reader with the ability to quickly review contaminant-specific information that is most ger-
mane to their particular contaminant-based inquiry. While the media for these investigations
vary widely (air, soil, sediments, groundwater, surface water, etc.), the available forensic
techniques are remarkably similar.
The basic structure of each contaminant-specific chapter was so devised that the reader
is provided with an overview of the chemistry of the contaminant, current analytical methods
used for detection, identification of natural and anthropogenic sources, and finally a presen-
tation of forensic techniques for consideration. As with many sciences, certain contaminants
are more studied and forensically evolved than others. Petroleum hydrocarbons, for example,
have decades of forensic technique development, as contrasted with the emerging contam-
inants, such as dioxins or perchlorate. The sophistication of the forensic technique is also
often a function of the global interest of the scientific community in a particular contaminant
or forensic technique. As a result, many forensic techniques are rapidly changing not only as
a function of their global interest but also due to their migration from an existing scientific field
or study. An example of this migration is the development of microbiological forensics. While
this scientific discipline is extensively employed in criminal and bioterrorism applications, it is
only recently being employed in environmental forensic investigations.
Another reason for the evolution of environmental forensics is rapid advances in analytical
methods, such as comprehensive gas chromatography, gas chromatography with isotopic
ratio mass spectrophometry, and laser ablation inductively coupled plasma mass spectrom-
etry, that provide greater analytical precision, lower detection limits, and a greater number
of contaminants to examine forensically. When used in concert, these techniques as well
as emerging statistical tools provide the forensic investigator with a multitude of possible
techniques for answering the forensic questions of contaminant age dating and origin.
It is our hope that the material in this book will be a useful contaminant-specific reference
and will nurture ideas for developing additional techniques for use by the environmental
forensic community. We wish you the greatest success in your environmental investigation
and in your contributions to this emerging science.
Robert .D Morrison, Ph.D.
Brian .L Murphy, Ph.D.
Contributors
EDITORS Robert D. Morrison, Ph.D. is a soil physicist with over 35 years of experience as an environ
mental consultant. Dr. Morrison has a B.S. in Geology, an M.S. in Environmental Studies, an
M.S. in Environmental Engineering, and a Ph.D. in Soil Physics from the University of Wis
consin at Madison. Dr. Morrison published the first book on environmental forensics in 1999,
is the editor of the Environmental Forensics Journal and is Director of the International Soci
ety of Environmental Forensics (ISEF). Dr. Morrison specializes in the use of environmental
forensics for contaminant age dating and source identification.
Brian L. Murphy, Ph.D. is a principal scientist at Exponent. He is the author of more than
30 journal publications and is on the editorial board of the journal Environmental Forensics.
Dr. Murphy has an Sc.B. from Brown University and M.S. and Ph.D. degrees from Yale
University in physics. Dr. Murphy has had Visiting Instructor positions at Harvard School of
Public Health and the University of South Florida. His practice focuses on reconstructing past
contaminating events, either for purpose of remedial cost allocation or in order to determine
doses in toxic torts.
CHAPTER AUTHORS Andrew S. Ball, Ph.D. is Foundation Chair in Environmental Biotechnology at Flinders
University of South Australia in Adelaide. Dr. Ball previously spent 16 years working at the
University of Essex in the United Kingdom. Environmental issues such as contaminated
land and water, climate change, and loss of biodiversity are key issues at both local and
international scales. His research is focused on the response, in terms of activity and diversity
of the microbial community, to environmental perturbations. One of his major interests is the
treatment of contaminated land and water.
Donna M. Beals attended the University of South Carolina as a marine science major, and
then attended graduate school at the University of California, Santa Cruz. Her research
involved the use of naturally occurring radionuclides to study ocean processes. Prior to joining
the Savannah River National Laboratory, she worked as a research chemist at a commercial
laboratory which provided analytical services to several Department of Energy sites, thereby
learning about the man-made radionuclides in the environment. Since joining the Savannah
River National Lab in 1991, Ms. Beals has been involved with developing very sensitive
analytical techniques for environmental monitoring and for nuclear forensic analyses. Her
publications cover the periodic table, from tritium to plutonium, from analytical method to
Instrument development, with sampling sites from the central Pacific gyre (near Hawaii) to
the Arctic Ocean.
Philip B. Bedient, Ph.D. is a recognized expert in surface-water and groundwater hydrol
ogy, simulation modeling, and the fate and transport of contaminants in the environment.
Dr. Bedient is Herman Brown Professor of Engineering and has authored four books and
more than 125 professional articles in the past 30 years. Dr. Bedient holds B.S., M.S., and
Ph.D. degrees from the University of Florida. He serves as an expert witness in toxic tort and
environmental litigation cases.
Laurie Benton, Ph.D. received a Ph.D. in Geosciences from the University of Tulsa in 1997
and an M.S. in Geochemistry from New Mexico Institute of Mining and Technology in 1991.
She has been an environmental consultant for 7 years at Exponent, Geraghty & Miller, and
the law firm of Gardere & Wynne. Prior to joining Exponent, Dr. Benton conducted isotopic
geochemistry research as a National Science Foundation postdoctoral fellow at the Carnegie
Institution of Washington, Department of Terrestrial Magnetism in Washington, DC.
Brad Besslnger, Ph.D. is a senior geochemist with Exponent in Lake Oswego, OR, and
specializes in environmental chemistry and the processes affecting the fate and transport of
organic compounds and metals in the environment. He received his Ph.D. from the University
of California at Berkeley in 2000, with a dissertation focused on the speciation and mobility
of metals such as mercury under hydrothermal conditions. His previous professional activ
ities include the development of conceptual and numerical models of mercury cycling and
bioaccumulation in the San Francisco Bay estuary, the evaluation of treatment alternatives
for mercury-contaminated soils and sediments, and the behavior of mercury spilled from gas
pressure regulators and mercury vapor in indoor air. Dr. Bessinger's analyses in the field
of environmental forensics have been used in a number of lawsuits concerned with source
allocation and exposure.
XX CONTRIBUTORS
Gary N. Bigham, LG, is a principal with Exponent in Bellevue, WA, and specializes in the
evaluation of contaminant and sediment transport and fate in the environment. He received
his B.S. in Geology from Oregon State and his M.S. in Geophysical Sciences from Georgia
Tech. Gary has undertaken several investigations of mercury in the environment and in indoor
air over the past 15 years. The largest has been the comprehensive remedial investigation of
mercury cycling and bioaccumulation in Onondaga Lake, NY. He also recently participated
in a natural resource damage assessment of the Guadalupe River, CA, which drains the
New Almaden Mining District, the largest mercury mining area in the United States. Over
the past ten years, he has been involved with litigation regarding the influence of nutrients
on mercury cycling and bioaccumulation in the Florida Everglades. Gary has participated in
investigations at many other mercury-contaminated sites and published numerous papers
and presentation abstracts. He also led an extensive evaluation of the behavior of mercury
spilled from gas pressure regulators and mercury vapor in indoor air and served as an expert
witness in litigation involving mercury spilled in buildings and homes.
Paul D. Boehm, Ph.D. is Group Vice President and Principal Scientist of Exponent's Environ
mental business. Dr. Boehm has devoted 28 years to environmental consulting experience
on chemical aspects of aquatic and terrestrial contamination. Dr. Boehm is a recognized envi
ronmental chemist and marine scientist; an originator of advanced techniques for petroleum
and PAH fingerprinting; a developer of the US "Mussel Watch" national monitoring program;
and an authority on fate/transport/effects of oil and chemical spills. His expertise includes
extensive knowledge of the strategic application and practice of environmental forensics
(chemical fingerprinting, fate/transport, source attribution, and allocation) using polycyclic
aromatic hydrocarbons (PAHs), polychlorinated biphenyls (PCBs), dioxins, and other tracers.
Dr. Boehm has been extensively involved in the Exxon Valdez oil spill science programs for
over 16 years. He has published more than 100 articles in peer-reviewed journals and has
been appointed to serve on several National Academy of Sciences panels.
Teresa S. Bowers, Ph.D. is environmental scientist with a Ph.D. in Geochemistry, with
experience in exposure, mathematical and geochemical modeling, and the application of this
information to risk-based environmental strategies. Dr. Bowers has worked as a consultant
at Gradient Corporation for 15 years, where she has developed blood lead and urine arsenic
models that relate human exposure to environmental sources of lead and arsenic. She has
also published unique statistical approaches to calculating soil cleanup levels for a variety
of contaminants. Prior to her work at Gradient, Dr. Bowers held research and visiting faculty
positions at the Massachusetts Institute of Technology and Harvard University, where she
taught courses in resource geology and applied thermodynamics.
Leigh A. Burgoyne, Ph.D. is a biochemist/molecular biologist at the School of Biological
Sciences, Flinders University in Adelaide, South Australia. Dr. Burgoyne has interests in the
degradation of DNA, chromatin structure, genome structures, and practical applications of
these fields. Dr. Burgoyne has extensively studied issues regarding forensic DNA issues and
the problems of long-term DNA storage. Dr. Burgoyne co-authored one of the first articles on
the use of forensic DNA issues in 1987 titled "Hypervariable lengths of human DNA associated
with a human satellite III sequence found in the 3.4kb Y-specific fragment' (Nucleic Acids
Research 15: 3929). Dr. Burgoyne also designed one of the earliest DNA storage materials
specifically designed to protect DNA and co-edited one of the earliest books on the topic,
DNA in Forensic Science (ISBN 0-13-217506-1), in 1990.
David E.A. Catcheside, Ph.D. is Professor of Genetics and Head of the School of Biolog
ical Sciences at Flinders University in Adelaide, South Australia. Dr. Catcheside's primary
research interest is the understanding of how information is exchanged between chromo
somes during meiotic recombination. In recent years, he has collaborated with Leigh Burgoyne
in developing novel DNA-based forensic tools.
Jeffrey R. Chiarenzelli, Ph.D. is a geologist and environmental scientist living and working
in northern New York. His research interests include fate, transport, and transformation of
polychlorinated biphenyls in the environment. Dr. Chiarenzelli's current projects include the
relationship between atmospheric deposition of contaminants and lake-effect precipitation,
and differentiating locally derived from far-traveled contaminants in the Arctic.
Jan H. Christensen, Ph.D. is assistant professor at the Department of Natural Sciences, The
Royal Veterinary and Agricultural University, Copenhagen, Denmark. His specialties include
oil spills in the manne and terresthal environment; oil spill identification; transport and trans
formation of petroleum hydrocarbon mixtures (e.g., crude oil and refined petroleum products);
chemical analysis of complex mixtures of contaminants in the environment (environmental
profiling) using modern analytical techniques; development of novel tools for automated chro
matographic preprocessing; chemometric data analysis of preprocessed analytical data (e.g.,
chromatographic data and fluorescence landscapes); statistical evaluation of sample simi
larities; fate of complex chemical mixtures in environmental samples; and risk assessment
of pollutant mixtures. Dr. Christensen manages a laboratory at the Royal Veterinary and
CONTRIBUTORS xxi
Agricultural University, Denmark, and has authored 36 publications on analytical chemistry
subjects.
Winnie Dejonghe, Ph.D. is a project manager within the Environmental and Process
Technology Centre of the Flemish Institute for Technological Research (VITO) in Belgium.
Dr. Dejonghe is involved in research concerning the remediation of contaminated soils and
aquifers through natural attenuation (aerobic and anaerobic removal of BTEX, CAH, heavy
metals, and pesticides) and the study of the microbial community structure by the use of
molecular techniques (RT-PCR-DGGE).
Richard E. Doherty, PE, LSP, is a PE in LSP and he holds an M.S. in Civil/Environmental
Engineering from the Massachusetts Institute of Technology and a B.S. from the University
of Lowell. Mr. Doherty has worked in the environmental investigation and remediation field
since 1987, and is the founder and President of Engineering & Consulting Resources, Inc.
(www.ecr-consulting.com). Mr. Doherty has extensively researched the history of use and
manufacturing of industrial/commercial chemicals, particularly chlorinated solvents. Articles
by Mr. Doherty on the subject of chlorinated solvents are recognized classic articles on this
subject. He is a Registered Professional Engineer in four states, and is a Massachusetts
Licensed Site Professional.
Gregory S. Douglas, Ph.D. has over 25 years of experience in the field of environmental
chemistry. He has designed, implemented, managed, audited, and defended a wide range of
environmental forensic chemistry studies for government and industry concerning complex
petroleum and fuel contamination issues in marine and soil/groundwater systems. Dr. Dou
glas has performed extensive research concerning the fate of gasoline NAPL and gasoline
additives in groundwater. He has written interpretive reports on more than 100 site or inci
dent investigations involving gasoline source and age dating issues, and has published and
presented on the development and application of environmental forensic analytical methods,
and source identification and allocation within complex contaminated environments.
P. Brent Duncan, Ph.D. has a B.A. in Geology (Earth Science) and Environmental Studies
from Baylor University, an M.S. in Environmental Science from Baylor University, and a Ph.D.
in Environmental Science from the University of North Texas. Recent emphasis has been in
freshwater systems, geographic information systems, and hydrologic modeling.
Arthur F. Eidson, Ph.D. is a chemist with 30 years of diversified experience studying the
interactions of metals with biological systems and assessing risks associated with environ
mental contaminants. He received a Batchelor of Science in Chemistry degree from the
University of Michigan and a Ph.D. from the University of Illinois, Chicago. While at the Inhala
tion Toxicology Research Institute (now named the Lovelace Respiratory Research Institute),
Dr. Eidson conducted field investigations and laboratory experiments on the biological fate
of inhaled industrial uranium and mixed uranium-plutonium aerosols by their physical and
chemical properties. Since 1991, he has managed risk assessments of radioactive, haz
ardous, and mixed-waste contamination for commercial chemical and oil company clients,
state environmental agencies, and governmental agencies, including the Federal Aviation
Administration, the US Department of Defense, and the US Department of Energy. He is a
member of the Society for Risk Analysis and the Health Physics Society, and served as a
member of the National Council on Radiation Protection and Measurements (NCRP), Task
Group-15 on Uranium.
Melanie R. Edwards received her M.S. in Statistics from the University of Wisconsin at
Madison in 1998 and a B.S. in mathematics from the University of Washington in 1991. She
has 12 years of experience in environmental consulting both as a statistician and as a data
manager. Her work ranges from preparing summary statistics for risk calculations to predicting
contaminant trends in biological tissues to evaluating results of relative bioavailability studies.
Merv Fingas, Ph.D. is Chief of the Emergencies, Science and Technology Division of Envi
ronment Canada. Dr. Fingas has a Ph.D. in Environmental Physics from McGill University and
three master degrees. His specialties include spill dynamics and behavior, spill-treating agent
studies, remote sensing and detection, in-situ burning, and the technology of personal pro
tection equipment. He has devoted the last 30 years of his life to spill research and has over
600 papers and publications in the field. Dr. Fingas is a member of several editohal boards
including being editor-in-chief of the Journal of Hazardous Materials, the leading scientific
journal covering chemical fate, behavior, and countermeasures.
A. Mohamad Ghazi, Ph.D. is an analytical geochemist with ERS Consulting, Atlanta, GA.
He has a bachelor's degree in Geology and Chemistry and a Ph.D. in Geology. Previously
he was Associate Professor of Geology and Director of the Laser Ablation Plasma Mass
Spectrometry (LA-ICPMS) at Georgia Sate University. Dr. Ghazi's areas of research are in
analytical and environmental geochemistry, with special focus in the field of forensic chemistry.
With more than 15 years of laboratory and classroom experience, in addition to classic
analytical chemistry techniques. Dr. Ghazi has made significant contributions in developing an
xxii CONTRIBUTORS
application of laser ablation for in-situ analysis of materials. Dr. Ghazi is the author of 65 peer
reviewed articles and principal investigator on 15 successful research proposals to National
Science Foundations and other private agencies. He is an honorary member of Sigma Xi
International Scientific Society and he sen/es on the editorial board for the International
Journal of Environmental Forensics.
Duane Graves, Ph.D. received a Ph.D. in Life Sciences from the University of Tennessee
and is currently a principal with GeoSyntec Consultants with over 20 years of research and
consulting experience. His professional practice areas include environmental biotechnology;
environmental forensics; in situ groundwater, soil, and sediment remediation; and detection
and remediation of biological contaminants. Dr. Graves organized and led the first large-
scale commercial application of real-time on-site polymerase chain reaction technology for
the detection of Bacillus anthracis in response to the 2001 bioterrorism attack launched
through the United States Postal Service. He is also actively involved in the development
of new bioremediation technologies and innovative sampling and analytical techniques for
environmental applications.
M. Coreen Hamilton, Ph.D. is an analytical chemist specializing in method development
for monitoring organic contaminants in the environment and in biological tissue samples.
Dr. Hamilton has been the senior scientist at AXYS Analytical for over 20 years, where she has
directed the research leading to the development of methods for the analysis for perfluorinated
chemicals, polybrominated diphenylethers, PCB congeners, brominated dioxins and furans,
and a variety of other compounds. In conjunction with the EPA Office of Water and her AXYS
colleagues, Dr. Hamilton assisted in the development of Method 1668A, for the analysis of
all 209 PCB congeners by high resolution GC/MS and EPA Method 1614 for brominated
diphenyl ethers. Dr. Hamilton is also an adjunct professor at the University of Victoria.
Betsy Henry, Ph.D. is a managing scientist at Exponent and has been working in the field
of mercury transport and fate for 15 years. She earned a Ph.D. from Harvard University
in 1992 with a dissertation on bacterial methylation of mercury in the environment. Her
main focus at Exponent has been complex mercury-contaminated sites including Onondaga
Lake in Syracuse, New York, and the VentronA/elsicol Superfund Site on Berry's Creek in
New Jersey. In addition to project management, she has designed and implemented studies
of mercury methylation and remineralization in lakes and mercury volatilization from soils.
She has also co-authored several published papers and abstracts on mercury cycling and
bioaccumulation in the environment and served on an expert review panel for investigations
at Lavaca Bay, another mercury-contaminated site.
Randy D. Horsak, PE, is a principal and President of 3TM International, Inc., an environmen
tal consulting firm in Houston, Texas, that specializes in environmental science, engineering,
and forensic investigations. Mr. Horsak has more than 30 years of professional experience
in environmental project management, multi-media sampling and analysis, engineering fea
sibility studies, and remediation. Mr. Horsak often serves as a consultant or testifying expert
in toxic tort and environmental litigation cases.
Jacqui Horswell, Ph.D. graduated from the University of Aberdeen in soil microbiology and
is currently a senior research scientist with ESR, Ltd in Poriru, New Zealand. Dr. Horswell
specializes in the investigation of microbial ecology of soils, soil biotechnology, and envi
ronmental contamination. Her primary research interest is the use of cultural and molecular
techniques to characterize soil microbial community structure and dynamics. Dr. Horswell
has published pivotal articles regarding the identification of microbial communities In soil and
their application in criminal and environmental forensic investigations.
Glenn W. Johnson, Ph.D. is Research Associate Professor at the Energy and Geoscience
Institute (EGI) at the University of Utah. His work at EGI includes research and application of
chemometric methods in environmental forensics; the study of sources, fate, and transport of
persistent organic pollutants; and teaching within the Department of Civil and Environmental
Engineering. Dr. Johnson is also President and Chief Scientist of GeoChem Metrix, a small
consulting company specializing in environmental forensic investigations for litigation support
projects.
Natalie Leys, Ph.D. is a project manager at the laboratory for microbiology at the Belgian
Nuclear Research Centre (SCK/CEN). Dr. Leys is the principal investigator of several research
projects studying the physiological and genetic response of heavy metal resistant Cupriavidus
metallidurans strains in different stress situations. Gene transfer, gene modifications, and
gene expression are analyzed in cells stressed by heavy metals, space flight, or related
parameters such as microgravity, cosmic radiation, UV-radiation, and vibrations.
Paul D. Lundegard, Ph.D. is a principal scientist with Unocal Corporation. Dr. Lundegard
received his Bachelor and Masters degrees in geology and his Ph.D. in Geochemistry from
the University of Texas at Austin. Paul is a geochemist with 28 years of experience in the
environmental and petroleum business. He has worked on a wide variety of contaminant
CONTRIBUTORS xxiii
fate and forensic issues at sites ranging from upstream exploration and production facilities
to downstream refining and marketing facilities. His litigation experience includes claims for
natural resource damages, cross-contamination, property value diminution, and human health
impacts.
James R. Millette, Ph.D. is a scientist with MVA Scientific Consultants in Atlanta, Geor
gia. Since 1972, Dr. Millette's research focus is the investigation of environmental toxicol
ogy/particles using electron microscopy techniques and has over 60 peer-reviewed articles
published on this subject. Dr. Millette's previous work included 11 years as a research sci
entist at the United States Environmental Protection Agency Research Center in Cincinnati,
Ohio, and 5 years at McCrone Environmental Services performing and supervising analysis
of particulates and product constituent analysis by microscopic techniques. Dr. Millette has
testified in court on several occasions concerning environmental lead-containing particles.
Stephen M. Mudge, Ph.D. is a senior lecturer in marine chemistry and environmental
forensics in the School of Ocean Sciences, University of Wales—Bangor, United Kingdom.
Dr. Mudge is responsible for developing the world's first undergraduate degree program
in Environmental Forensics and has worked for many years on the application of forensic
techniques to track sewage and other organic matter in the environment, including the use
of biomarkers, and interpreting and linking these results with multivariate statistical meth
ods. Dr. Mudge has published extensively and is considered a world leader in the field of
environmental forensics.
Rachel A. Parkinson, Ph.D. is a molecular microbiologist with a B.Sc. in Microbiology and
Biochemistry from the University of Otago in New Zealand and received an M.Sc. (Honors)
in Cell and Molecular Biology from Victoria University of Wellington in New Zealand. Ms.
Parkinson's primary research focus is the use of non-human DNA forensic applications.
Priyabrata Pattnaik, Ph.D. received his B.Sc. in Zoology with distinction from Utkal Univer
sity in Bhubaneswar, India, an M.Sc. (microbiology) from Orissa University of Agriculture and
Technology, in Bhubaneswar, and a Ph.D. in microbiology from the National Dairy Research
Institute in Karnal, India. Dr. Pattnaik served at the International Centre for Genetic Engi
neering and Biotechnology in New Delhi, where he worked on the development of a malaria
vaccine. Dr. Pattnaik is also the recipient of the young scientist award-2000 from the Asso
ciation of Microbiologists of India and has more than 50 publications to his credit. Currently
Dr. Pattnaik is working as staff scientist at Defense Research and Development Establish
ment in Gwalior, India. His research interest is recombinant sub-unit vaccines, bioprocess
scale-up and receptor-llgand interaction involved in biology and pathogenesis.
loana G. Petrisor, Ph.D. has a Ph.D. in Biology/Environmental Biotechnology from Roma
nian Academy of Sciences (awarded in 2000) and a Bachelor degree in Chemistry with a
major in Biochemistry from Bucharest University in Romania, Faculty of Chemistry (awarded
in 1992). In December 1999, she completed a UNESCO training program on Plant Molecular
Genetics at the University of Queensland, Department of Botany in Brisbane, Australia. She is
co-author of 63 scientific papers published in peer-review journals and proceedings. Dr. Petrisor
is the managing editor for the Environmental Forensics Journal an6 a member of the editorial
board of several other peer-review journals. She was recently elected as vice-chairman of the
newly formed ASTM sub-committee on Forensic Environmental Investigations. She Is a member
of ACE (American Chemical Society), AEHS (Association for Environmental Health and Sci
ence), ITRC (Interstate Technology Regulatory Council), and other professional organizations.
Her work experience includes conducting innovative research (at lab, field, and pilot scales)
for the United States Department of Energy and the European Community on bioremediation,
phytoremediation, environmental characterization, and risk assessment, as well as forensic
investigations on petroleum products, chlorinated solvents, and heavy metal releases.
John F. Quensen, III, Ph.D., is a research professor in the Department of Crop and Soil
Sciences at Michigan State University. His research interests include both aerobic and anaer
obic microbial transformations of normally recalcitrant environmental contaminants Including
polychlorinated biphenyls, dioxins, and pesticides, and the biological effects of microbial
metabolites of these compounds. He was the first scientist to demonstrate the microbially
mediated reductive dechlorination of PCBs and the DDT metabolite DDE.
Kim Reynolds Reid is an environmental chemist with 13 years of experience in evaluating
and interpreting analytical data. As a consultant at Gradient Corporation, she applies her
knowledge of analytical techniques to the usability and integrity of inorganic, wet chemistry,
and organic data generated in support of human health and ecological risk assessments,
environmental forensic studies, and litigation matters. Ms. Reid also designs and provides
quality assurance oversight for a wide variety of sampling and laboratory analysis programs.
Prior to joining Gradient, Ms. Reid was an inorganic analyst at Enseco, Inc.
Jennifer K. Saxe is a consulting environmental engineer at Gradient Corporation whose
work focuses on evaluating and modeling the environmental transport, transformation, and
xxiv CONTRIBUTORS
ecological bioavailability of trace elements and hydrophobic organic compounds in soil and
water, as well as their exposure to organisms. She also has experience in designing and eval
uating chemical characterization studies for environmental media containing these analytes.
Prior to becoming a consultant, Dr. Saxe worked in the United States Environmental Pro
tection Agency Office of Research and Development, National Risk Management Research
Laboratory. She works and resides near Boston, Massachusetts.
Walter J. Shields, Ph.D. received his Ph.D. in soil science from the University of Wisconsin
at Madison in 1979. He conducted research on land applications of biosolids and herbicide
impacts to watersheds as an environmental scientist with Crown Zellerbach Corporation until
1985. He has been an environmental consultant since then, first with CH2M Hill and then
with Exponent, where he is currently Director of the Environmental Sciences. Dr. Shields has
testified as an expert in source identification related to toxic tort and cost allocation cases,
and in the timing of releases in insurance coverage cases.
Scott A. Stout, Ph.D. is an organic geochemist with 19 years of petroleum and coal industry
experience. He has extensive knowledge of the chemical compositions and chemical fingerprint
ing applications of coal, petroleum, gasoline, and other fuel-derived sources of contamination
in terrestrial and marine environments. Dr. Stout has written interpretive reports on more
than 250 site or incident investigations and has authored or co-authored nearly 100 papers
published in scientific journals and books. He has conducted environmental research while
employed at Unocal Corporation, Battelle Memorial Institute, and is currently a partner at
NewFields Environmental Forensics Practice, Rockland, Massachusetts.
Julie K. Sueker, Ph.D., P.H., PE, is a hydrogeochemist with more than 13 years of profes
sional experience in physical hydrology, isotope hydrology, hydrogeology, and environmental
geochemistry. Dr. Sueker's hydrology experience includes determining sources of solutes
in surface- and groundwater-environments using chemical and isotopic tracers, assessing
and modeling the transport and fate of solutes in surface- and groundwater-environments,
and predicting flow paths of water by using chemical and isotopic hydrograph separation
techniques. Dr. Sueker's forensics focus is the use of isotopes to distinguish sources of con
stituents of concern (COCs) in the environment and to demonstrate microbial degradation of
COCs in both regulatory and litigation contexts.
F. Ben Thomas, Ph.D. is a principal and Vice President at Risk Assessment and Management
Group, Inc. (RAM Group), an environmental and health consulting firm in Houston, Texas.
Dr. Thomas's professional training is in pathology and toxicology, and he has over 25 years
of experience in the adverse effects associated with chemical and physical toxicants. Other
focuses of his consulting practice include risk assessment, decision analysis, strategic plan
ning, program development, regulatory negotiation, and program management. Dr. Thomas
often serves as a consulting and/or testifying expert in toxic tort and environmental litigation
cases.
Yves Tondeur, Ph.D. received his Ph.D. in Chemistry from the Free University of Brus
sels, Belgium. Although his formal education related to the field of physical organic chem
istry. Dr. Yondeur did postdoctoral research work in environmental trace analyses involving
polychlorinated dibenzo-p-dioxins and polychlorinated dibenzofurans (PCDD/Fs) and other
persistent organic pollutants at Florida State University and then with the National Institute
of Environmental Health Sciences. Dr. Tondeur developed the United States Environmen
tal Protection Agency Method 8290 for PCDD/Fs in 1987. He is founder of Alta Analytical
Perspectives located in Wilmington, North Carolina, where he serves as president and CEO.
Allen D. Uhler, Ph.D. has over 25 years experience in environmental chemistry. Dr. Uhler
has developed advanced analytical methods for petroleum, coal-derived, and anthropogenic
hydrocarbons, and other man-made organic compounds in waters, soils, sediments, vapor,
and air. He has conducted assessments of the occurrence, sources, and fate of fugitive
petroleum at refineries, offshore oil and gas production platforms, bulk petroleum storage
facilities, along petroleum pipelines, at varied industrial facilities, and in sedimentary envi
ronments. Dr. Uhler has studied coal-dehved wastes at former gas plants, wood-treating
facilities, and in nearby sedimentary environments. His experience includes expertise in the
measurement and environmental chemistry of man-made industrial chemicals including PCB
congeners and Aroclors, persistent pesticides, dioxins and furans, metals, and organometallic
compounds.
Karolien Vanbroekhoven, Ph.D. is a researcher and project manager within the Environ
mental and Process Technology Centre of Expertise of the Flemish Institute for Technological
Research (VITO) in Belgium. Dr. Vanbrokehoven specializes in microbiology, molecular ecol
ogy, and chemistry. Dr. Vanbroekhoven has 6 years of experience in soil and groundwater
remediation and is involved in the development of technologies for the removal of heavy
metals from groundwater and contaminated soils (both by in situ bioprecipitatlon and abiotic
techniques).
CONTRIBUTORS xxv
Drew R. Van Orden, PE, is a senior scientist at RJ Lee Group, Inc., where he has been
involved in asbestos research for the past 18 years. Mr. Van Orden was educated at
Millersville State College, where he earned a B.A. in Earth Sciences; at the Pennsylvania
State University, where he earned an MS in Mineral Process Engineering; and at the Uni
versity of Pittsburgh, where he earned an M.A. in Applied Statistics. He is a Professional
Engineer (Mineral Engineering) in the Commonwealth of Pennsylvania. Mr. Van Orden has
authored or co-authored numerous articles on asbestos analyses and is an active participant
in asbestos analytical methodology development.
Emily A. Vavricka is a geologist with DPRA. Ms. Vavricka specializes in the investigation
and forensic determination of perchlorate in soil and groundwater. Ms Vavricka has investi
gated the sources of naturally occurring perchlorate in southern California and has examined
forensic techniques for distinguishing between naturally occurring and anthropogenic sources
of perchlorate. Ms. Vavricka has a B.S. in Environmental Studies from the University of
California at Riverside.
Zhendi Wang, Ph.D. is a senior research scientist and Head of Oil Spill Research of Envi
ronment Canada, working in the oil and toxic chemical spill research field. His specialties
and research interests include development of oil spill fingerprinting and tracing technology;
environmental forensics of oil spill; oil properties, fate, and behavior of oil and other hazardous
organics in the environment; oil burn emission and products study; oil bioremediation; identi
fication and characterization of oil hydrocarbons; spill treatment studies; and applications of
modern analytical techniques to oil spill studies and other environmental science and technol
ogy. Dr. Wang has authored 270 academic publications including 76 peer-reviewed articles
and 4 invited reviews in highly respected journals within environmental science and analyt
ical chemistry, and 8 books and book chapters. Dr. Wang has received numerous national
and international scientific honors. He is editorial board member of Environmental Forensics
and had been guest editor for several journals. He has been invited by many international
agencies (such as UNDP, UNEP, UNIAEA, lOC/UNISCO, APEC, US EPA, US MMS, ASTM,
CCME, and Canadian International Development Agency) and many countries to conduct
numerous workshops and give seminars.
James M. Waters, Ph.D. graduated from Flinders University in Adelaide, South Australia.
His dissertation examined ways in which soil microbial communities could be compared by
DNA profiling methods. He is currently a postdoctoral researcher at the University of Durham
investigating epithelial stem cells.
Chun Yang, Ph.D. is a scientist with the Environmental Technology Center at Environment
Canada. He received Ph.D. from Nanyang Technological University in Singapore and currently
specializes in the use of forensic analysis using a variety of analytical techniques. His primary
scientific interest is in the use of chemical fingerprinting for petroleum hydrocarbons to identify
the source of a release into the environment. He has authored or co-authored over 25 peer-
reviewed journals.
1
Mercury
Gary N. Bigham, Betsy Henry, and Brad Bessinger
nr
u
1.6 iffiK^marf^fflw^ ii
•• ;?
MERCURY
1.1 INTRODUCTION tion of 0.002-0.005 |JLg/m^ reported in Table 1.1.1 (Seigneur
Mercury is a naturally occurring element that exists in et al., 1994). Although slow evaporation kinetics and ven
three oxidation states: Hg(0) (Hg^, elemental mercury), tilation will necessarily reduce concentrations in indoor
HgO) (Hg^, mercurous mercury), and Hg(II) (Hg^^, mer environments where mercury spills have occurred (Winter,
curic mercury). Of the three forms, only elemental mercury 2003), measurements between 0.5 (Carpi and Chen, 2001)
and mercuric mercury contribute to the global mass bal and 140 [ig/nr' (Smart, 1986) have been observed.
ance (the rarity of Hg(I) compounds can be explained by The fate and transport of elemental mercury released to
the instability of Hg-Hg bonds that characterize the Hg(I) the atmosphere are conceptualized in Figure 1.1.1. Consis
forms). Although mercury is nondegradable, it readily con tent with Table 1.1.1, Figure 1.1.1 shows that gaseous ele
verts between the oxidation states and chemical species mental mercury is the predominant species in outdoor air,
listed in Table 1.1.1. Chemical transformations between accounting for as much as 98 percent of the total elemen
forms govern the fate and transport of elemental mercury tal mass. This speciation is partially attributed to mercury's
in the atmosphere. The production of mercuric methylmer- high saturated vapor pressure. (Because gaseous elemental
cury (CHsHg^) in aqueous environments is similarly mercury concentrations are significantly below saturation
dependent. with respect to the liquid form, atmospheric releases are
thermodynamically restricted from converting to Hg^(/).)
Other chemical properties that contribute to the stability of
1.1.1 Elemental Mercury gaseous elemental mercury in the atmosphere include its
Zero-valent elemental mercury (Hg(0)) occurs as a liquid low water solubility (which prevents it from being quickly
(Hg^(/)), gas (Hg^ {g)), and dissolved constituent in water removed by precipitation via the chemical species Hg^(aq))
(Hg^(fl^)) at ambient temperatures (Table 1.1.1). Owing to and its high ionization potential (which inhibits its oxida
its relatively high (for a metal) saturation vapor pressure, tion to reactive gaseous mercury (Hg(II)), a species with a
the gaseous concentration in equilibrium with the liquid is higher water solubility and rate of sequestration, by cloud
predicted to be 13,000|jLg/m^ (Winter, 2003). This concen droplets and precipitating aerosols) (Mason et aL, 1994).
tration is three orders of magnitude higher than the time- From a forensic science perspective, the most impor
weighted average threshold limit value of 25 |JLg/m^ used for tant transformation of elemental mercury depicted in
occupational exposure (ACGIH, 2000). It is also sbc orders of Figure 1.1.1 is its conversion to mercuric mercury, a species
magnitude higher than the reported background concentra that is readily deposited and potentially transported to
Table 1.1.1 Typical Mercury Species and Concentrations of Mercury Species in Gas and Water
Phases in the Atmosphere
Oxidation State Phase Atmospheric Concentration'^ Species^""
Hg(0) Liquid Hg°(/)
Gas 0.002-0.005 ^ig/m^ ^g\g)
Water 6-27xlO-Vg/L Hg^iaq)
Hg(D Water Hg2^'
Hg(II)''-^ Solid^ g HgS(5), HgO(5), Hg(0H)2(s),
HgCl.(5), HgSe(s), HgS04(s),
(CH3)HgCl(s),
>0Hg^>SHg',(>S)2Hg^
>SCH3Hg^'
Liquid^ (CH3).Hg(/), (C2H5)2Hg(/)
Gas 0.9-1.9 X 10-Vg/m^ HgiORhig), HgChigh CH^ngClig),
CH.HgCn.ig)
Water 0.4-1.3 X 10-Vg/L' Hg-\
Hg(OH) \ Hg(0H)2(fl^),
HgOHCl(fl^),
HgCr, HgCl. iaq), HgOf, }lgC\,-\
HgSOsiaq), Hg(S03)2-'.
HgC204(a^),
HgHS*, Hg(HS)2(a^). HgHS2-, HgS {aq).
ROHg*. RSHg", (RS)2Hg(a(7)
CH^Hg', (CH3)2Hg(a^)
''Atmospheric concentrations in gas and water phases from Seigneur et al. (1994) (where \Lg represents micrograms).
''Typical species reported in air from lin and Pehkonen (1999). water from Hintelmann et al. (1997), Benoit et al. (1999,
2001), and Haitzer et al (2002, 2003) (polysulfides in groundwater not included [Paquette and Helz, 1997; Jay et al,
2000]), and soil/sediment from API (2004).
'^Note that air, water, and sediment each contain multiple phases (gas. water, and solid).
'^">" refers to surface adsorption sites for mercury (e.g.. carboxyl and sulfide sites on soot and organic material).
^ "R" designates a natural organic ligand such as a humic and fulvic acid.
^HgS(s) is the most abundant naturally occurring form.
^HgO may be present in the solid particulate phase (Seigneur et a/., 1994).
^ Not significant in concentration.
' A large fraction of the mercury concentration dissolved in water droplets in the atmosphere is associated with soot
particles (Petersen et al, 1995).